Sulpho fatty body



Patented Nov 12, 19 35 v UNITED s ArEs' SULPHO ram nonY Melvin DeGroote, St. Louis, and Bernhard new.

Webster Groves. Mo., as'signors to lite Company, Webster Groves, Mo acorpora on of Missouri a No Drawing. ApplicatiomDecember 31, 1934, I

. Serial No. 769,026

,7 Claims. (01. iii-1e) This invention relates to a new'sulpho-fattybody and to a method of producing the same.

One object of our invention is to provide a new material, composition ofmatter, or chemical com- 8 pound, that is capable of various industrialuses, but particularly adapted for use as a substitute for Turkeyred oiland the like. Said new material, composition of matter, or chemicalcompound, may properly be described as a sulphofatty body derivedby'sulphonation of a split unsaturated fatty acid material having atleast 6 carbon atoms and less than 16 carbon atoms in the molecule andderived by the thermal decomposition of a body obtained by oxidation ofa rel atively highly unsaturated fatty body. Briefly, said new materialmay be described as a sulphofatty body derived by the sulphation orsulphonation of certain isologues or homologues of normal hendecenoicacid. The substance or substances sulphonated or sulphated to produceour new material are described in our co-pending application for PatentSerial No. 760,025, flied December 31, 1934. The raw materialemployed'in the sulphonation process and the method of pre-' l paringthe same are best described by reference to its homologues or isologues,such as normal hendecenoic acid and oleic acid.

Hendecenoic acid is obtained by distilling rlcinoleic acid or theglyceride thereof (castor oil) under diminished or atmospheric pressure.It is sometimes known as undecylenic acid.- The method of producing thisacid is 'well known and is described in the publlcation "Dictionary ofApplied, Chemistry", by Thorpe, 1922. 111 volume 4, pages 630 and 631 ofthe said publication the'reaction of hendecenoic 'acid is properlyindicated as follows:

but in the text the term hendecatolc-acid" is erroneously used to referto the product CnHzoOa. However,-volume 3, pape 515 of the saidpublication properly identifies hendecatoic acid is u'ndecyclic acid(CuHaeOz). In otherwords, the pyrolytic decomposition of ricinolelc acidor castor oil causes the molecule. to break at the hydroxyl position andyields a sulphonatable unsaturated "fatty" acid having 11 carbon atoms.It is understood'that the expression fatty ishere used because the splitacid thus obtained is a lower homologue of oleic-acid. However, so faras we are aware, this acid does not occur naturally in 1 any fat or oil.For reasons which will be subsequently obvious, we shall. refer tohendecenoic yea.

acid derived from castorpil as normal hendecenoic acid. 9 In ouraforementioned co-pending application we have described the productionof materials similar to ricinoleic acid insofar that they con- 5 tain anethylene linkage and. a hydroxyl radical in the hydrocarbon fatty chain.Briefly stated, the process there described -consists in subjecting arelatively highly unsaturated fatty acid or fatty body having an iodinenumber of 120, or higher, 10

and derived from the class of semi-drying, drying e I and marine oils tooxidation or blowing with air, particularly moist air, so as to decreasethe iodine number to or of its original value, with a subsequentincrease in acetyl value, or at least 15,

with the fori nation of bay bodies. Unsaturated oxidized bodies, soproduced, are then subjected- ,to thermal decomposition to yieldhomologues or isologues of normal hendecenoic acid in the same manneressentially that normal hendecenoic acid is derived from ricinoleic acidor from castor oil.

It is immaterial whether the products thus obtained are in the form 'offatty acids, or in the form of glycerides or a mixture of the same,

and it is immaterial whether the relatively highly unsaturated material,prior to oxidation; be in the form of a fatty acid or a glyceride or, amixture of same.

The raw material that we prefer to use in producing the new sulpho-fattybodies that consti- 80 .tute the subject-matter of our presentapplication for patent, is derived by the thermal decomposition ofoxidized or blown marine oils, particularly sardine oil. In order thatsaid raw material may be readily prepared without reference to any othersource of information, we give the following procedure for preparingsaid raw material: The blowing process and the thermal decomposition arepreferably conducted in the same vessel, pure-'- ly as a matter ofconvenience. Our preference. is i to employ 500 or 1,000 lbs. of sardineoil, blow the same with moist air at approximately 150 to 250 9 untilthere is a drop in iodine number to approx- 7 imately or $9 of theoriginal iodine value, and

.a rise in acetyl value or. absorption of oxygen corresponding to thedrop in the iodine value. .At

the completion of the blowing process the moist air'is shut ofl and thetemperature I with slightly reduced pressure, so as to thermally-de- 5ocompose the oxidized sardine oil. The aldehyde q like materialswhich'distill over are condensed and employed for any suitable purpose.'Ihe loss in-weight of the residue during thermal decomposition shouldnot exceed, as a rule, 10% or acid can be subjected to sulpho ation inthe various manners applied in the its higher homologue, oleic acid. 0

Itgis well known that oleic acid may be sulphonated at a relatively lowtemperature, for instance, or less, with66 Baum sulphuric acid to yielda fatty acid sulphate, i. e. oleic acid hydrogen hydrogen sulphate. Italso known phonation of that oleic acid may be sulphonated at or nearthe boiling point of water with sulphuric acid, or at a lowertemperature with an onium compound of sulphuric acid to yield a truesulphonic acid. Such true'sulphonic acids are differentiated from fattyacid sulphates above referred to by the fact that they do not decomposeon boiling with dilute hydrochloric acid. Another-well known procedurefor sulphonating oleic acid, is to sulphonate in the presence of asuitable aromatic compound, such as benzene, phenol, naphthalene betanaphthol, etc., so as to produce a sulpho aromatic fatty" acid.

tached to the aromatic nucleus and not directly to the hydrocarbon fattychain 'of the fatty ,acid. Although one can produce puresulpholeicfacid,

i. e., oleic acid hydrogen hydrogen sulphate,- yet.

the expression sulpholeic acid is most commonly employed in the arts toindicate the commercial product obtained by sulphation or sulphonationof oleic acid which contains, for example, not

. tones may be present.

only oleic acid hydrogen sulphate, but also the hydrolytic decompositionproduct, i. e., lrvdroxystearic acid, and also products obtained by theauto-esteriflcation of hydrox ystearic acid, such as hydroxystearylhydroxystearic acid. Unreacted oleic acid or its ester derived byreaction 'with hydroxystearic acid may be present. Lac- Sulphonated polyacids may be present. Sulpholeic acid may be almost free fromsulphur-containing constituents. Similarly, the sulphonation employed inthe manu- 'facture of a true sulphonic acid or asulphoaromatic fattyacid, is accompanied by similar hydrolytic decomposition products andother products obtained by the esterification of or etherization of thehydronla'ted bodies present. In the same manner that the expressionsulpholeic acid has been used broadly to indicate sulpho derivativesobtained by all three of these processes, together with the accompanyingmaterials, similarly the expression "normal sulphohendecenoic acid" isherein employed in the same analogous manner to indicate the analogousproducts obtained from normal hendecenoic acid alone or in presence ofsuch reactive aromatic compounds as benzene, phenol, naphthalene. betanaphthol, etc.

The unsaturated fatty acids employed as raw materials to produce thesulpho-fatty acids herein described} are characterized by having "atleast 6 carbon atoms and less than 16 carbon atoms,

'and being free or substantially so from -hende--' cenoic acid. Aspreviously stated, they represent isologues or homologues of normalhende-- cenoic acid and enter into the above three types of sulphonationor sulphation which has been described in respect to oleic acid andnormal Such sulphonation products are. characterized by the presence ofa sulphonic acid radical, but said sulphonic .acid radical is atphoisohomohendecenoic acid.

hendecenoic acid. Sin'e the exact composition of the raw materials areunknown except to the extent that they are unsaturated fatty acidshaving less than 16 carbon atoms and more than I 5 6 carbon atoms-in themolecule, one cannot exactly state their chemical composition, except asnoted that they may be sulphated or sulphonated to'produce sulphonicacids, fatty acid sulphates or sulpho-aromatics. Furthermore,- there arecertain hydrolytic reactions which take place during sulphonation withthe formation of hydroxy acids, and said-hydroxy acids react further to'give lactones, poly acids, etc.- In the same analogous manner as is truein the sulphbnation or sulph'ation of normal'hend'ecenoic acid or oleicacid. Various salts, esters, etc. may be formed from the sulpho bodiesin the usual manner, i. e., one may produce water-soluble salts, such assodium salts, potassium salts, ammonium salts, or salts derived dro'mbasic amines, such as; triethanolamine, water-insoluble calcium' salts,etc. Esters may be formed, such as ethyl ester, methyl ester,propyl'ester, butyl ester, etc. a

Purely for-the sake of convenience wewill refer to the raw material,prior to sulphonation, as

"isohomohendecenoic acid, because, in view of the method of preparation,and in view of the chemical reactions which these raw materialssoundergo, they appear to be isologues or homologues of hendecenoic acid,and therefore, in the absence of more suitable nomenclature, the coinedword isohomohendecenoic acid will be employed. Similarly, the newcomposition of 85 matter forming the subject-matter ofthe presentapplication for patent will be referred to as "sulpho-isohomohendecenoicacid". The word "sulpho is employed in the same manner that the word"sulpholeic acid is commonly employed 40 in the arts, 1. e., to meantheproduct obtained by sulphonation in any of the various mannersdescribed, plus the accompanying produQtPand not to mean the fatty acidsulphate derived at low temperature, which might also be'termed sul-What is said in our co-pendlng application for patent Serial No.760,024, filed Dec. 31, 1934, in

; regard to the sulphonation of normal hendecenoic acid, applies in ananalogous manner to the sulphonation of isohomohendecenoic acid hereincontemplated. In the said co-pending application-there appears thefollowing statement in regard to the sulphonation of normal hendecenoicacid: L

Thesulphbnation of-hendecenoic acid must behandled cautiously so as toprevent polymeramount of a readily sulphonatable aromatic compound, suchas phenol, is also a suitable pro- Whenthe sulphonated mass obtained bysulphonation in absence of an aromatic compound, isdiluted with waterthere is a decomposition or hydrolysis of some of the, fatty acidsulphate if present. The fatty acid sulphate referred tois hendecenoicacid,hydrogen hydrogen sulphate,

whichmayalsobechatacmlM-aumbstih-IS and may be consideredhydrogensulphate hendecoic acid, i. e., an acid in which one hydrogen ofhendecoic acid (undecylic acid). has been re- I placed by a hydrogensulphate radical. Thus,

the decomposition product obtained by hydrol ysis of hydrogen sulphatehendecoic acid is hydroxy hendecoic acid, and the poly acid obtained byautoesteriflcation. of two moles, of hydroxy hendecoic acid is'hydroxyhendecoyl hydroxy hendecoic acid. Thefanalogyto the formation ofhydroxyste'aric acid, poly acids, lactones, sulphated poly acids, etc.therefrom is evident".

What has been saidin the above-mentioned excerpt from our co-pendingapplication for patent Serial No. 760,024, filed December 31, 1934, inregard to the 'sulphatlon or sulphonation of normal handecenoic acid oritsKesters, applies with equal force and effect to the "sulphationorsulphonation of isohomohendecenoic acid, as is herein described. Thesame analogous sulphation or sulphonation reactions take place; the sameanalogous hydrolytic reactions take place;

the same analogous esterification or polymerization reactions takeplace: and the same anal gous compounds are formed, but are differentisomerically and probably different in the number of carbon atomspresent also.

It is well known that when reagents such as sulphoisohomohendecenoic'acid are prepared and have both a carbon] hydrogen and a sulphonichydrogen that only the sulphonic hydrogen need be neutralized ifdesired. Thus, one

5 may produce ahalf salt in which the carbon! 7 hydrogen isunneutralized; but one may also produce mixed salts, in which thesulphonic hydrogen is replaced by one metallic tom, such as Turkey redoil, as previously stated, and they may. also be used as a demulsifyingagent in the reso-,

- lution of crude petroleum emulsions of the water- I in-oil type. Ithas been so common to use a... demulsifying agent derived from an esterin the form of a salt, or in the form of an est'er,-that the expressionacid body isjrequently used to mean the acid itself or an ester thereof,or a salt thereof. The word body is herein employed in this same sensein conformity with its'prior usage in the art. v It is to be understood,that isohomohendecenoic acid, i. e., the product which is subjected tosulphonation or sulphation, need not. be derived from rdine oil, but maybe derived from" any 18 marln oil of commerce or from any semi-drying ordrying fatty oil or the corresponding. fatty acid. Sardine oil ispreferably employed because of its low cost, uniformity and easeofoxidation. It should also be understood that the sulphona- 20 tionof theisohomohendecenoic'acid or the split acid derived from oxidized sardineoil,.'need not be conducted in the manner above described togive fattyacid sulphates, but it may be conducted in a mannerso that the sulphoderivative 25' is in the. form of a true sulphonic acid or in the formofa sulpho-aromatic fatty acid. D Having thus described our invention,what we claim as new and desire to secure by Letters Patent is:

1. A new composition of matter, .consisting of 'a sulpho derivative ofan unsaturated,'saponiilable, fatty acid material, said unsaturated,'sa-' .poniflable, fatty acid material having at least 6 I carbon atomsand less than 16 carbon atoms in 85 the molecule, and derived by thermaldecomposodium atom, and the carboxylic drogen isre- 40 placed by somedissimilar atom or radical, such as an ammonium radical. Similarly; onemay produce a mixed ester, etc.

'Since isohomohendecenoic acid is-sulphated or sulphonated in the samemanner as oleic acid.

or normal hendecenoic acid, the sulphation or sulphonation' of whichincidentally is described in our first. mentioned co-pendingapplication, and also in U. S. Patent No. 1,749,463, to Bertsch, datedMay 4, 1930, it hardly appears necessary to desEribe the manufacture ofthe newcomposltion of a body. obtained by the oxidation of a relativelyhighly unsaturated ,fatty body; said fatty body, prior to oxidation,being characterized by an iodine number of not less than 120 and 40 notmore than 190, said oxidation being conducted at a temperature range offrom 150 C. to 250 C.,'by means of air until there is a drop intheiodine number to a value of not over two-thirds the original iodinenumber anda corresponding 4! sltion of matter, because it is only,necessary to applysuch conventional processes to. the raw materialdescribed in our last mentioned co-pending application and which haspreviously been briefly summarized. However, as an example, we

will state that we prefer to obtain 500 lbs. of

isohomohendecenoic acid derived by the thermaldecomposition of oxidizedsardine oil, prepared sis-previously described, and mix the same with150 lbs. of acetic anhydride, and then sulphonate the same with 500 lbs.of concentrated sulphuric acid at a temperature of not over 10 C. Thereaction mixture resulting from said sulphonation 5 or sulphationprocess is-washed in the cold with twice its volume of concentratedGlauberls salt solution, and after complete separation, the uptralizedwith .ammonium hydroxide, so that the 70 final mixture is an ammoniumsodium .salt'of a kind wherein'the sulphonic hydrogen is replaced by asodium ato'm'and the carboxylic hydrogen increasein the acetyl value;and said thermal decomposition being conducted at a temperature range offrom 270 C. to 330 C., with a loss in weight of not over 12%.

2. A new composition of matter, consisting of, an acidic, sulphoderivative of an unsaturated," saponifiable, fatty acid material; saidunsaturated, saponifiable, fatty acid material having. at least 6 carbonatoms, and less than 16 carbon atoms in the molecule, and derived bythermal decomposition of a body obtained by the oxida-' tion' of arelatively highly unsaturatedfatty body; said-fattybody, prior tooxidation, being characterized by an iodine number of not less than 120and not-more than .190, said oxidation being conducted at a temperaturerange offrom 150 C. to 250 0., by means of air until there is a dropin'the iodine number toa valueof not over two-thirds the original iodinenumber and a corresponding increase in the acetyl value: and

said thermal decomposition being conducted at a a O 9 per layer iswithdrawn and at least partially neuwtemperamre range of from 270 to 330rated, saponiilable, fatty acid material:v said 1111- at least partiallyreplaced by an ammonium radical.

Such may be used assubstitutes for I saturated, saponiflable, fatty acidmaterial having v at least 6 carbon atoms andJess than-'16 carbon atomsin the molecule, and derived by thermal decomposition oi abody obtainedby the oxidation 76 l of a relatively highly unsaturated fatty bodyasaid fatty body, prior to oxidation, bein'g char--' 'acterized by aniodine number of notless than 120 and not more than 190, said oxidationbein conducted at a temperature range of from 150 C. to 250. (2., bymeans ofair=until'there is a drop inthe iodine number to.a value-pf notover, twothirds the original iodine number and a corresponding increasein the acetyl- -value;- and said V k a drop in the iodine numberto avalue of notover two-thirds the original iodine number and acorresponding increase in the acetyl value; and said thermaldecomposition being conducted at a temperature range of from 270 C. to330 0., with s a loss in weight of not over 12%, neutralization beingaccomplished by means of an inorganic 6. A newcomposition' of matter,consisting of a 5- 150; C. to 250 C; by means of air until there-isthermal decomposition being conducted at a'temperature range of from 270C;-to-330--C.,'with a loss in weight of not over 12%;

4. A new. composition of matter, consisting of' a neutralizedsulpho-derivat-ive of anunsaturated, saponiflable, fatty acid-material;said-.un- Y saturated, saponifiable, fatty acid material havingoxidation of sardine 0 S id Oxidation being at least 6 carbonatoms andless*than 1 6 carbon 1- conductedat a temperature range of from 150 C.atoms in the molecule, and derived by thermal 250" Q, by means of airuntil there is a drop decomposition of abodypbtainedby the oxidationiniodin, number to a value of not over twoof a relativelyhighlyun'saturated fatty body; sa d fatty body. prior-to oxidation,being characterized by an iodine number of not less than '120 andrnotmore than ,l9 0, =said oxidation being. conducted; at a temperaturerange of from 150 C. to 250 6.; by means of air until there is a drop inthe-iodine number -to a value of not over twoehhfdS-the original iodinenumber and a corresponding in creaseiin the acetyl value; and saidthermal decomposition being conducted at a temperature 30" range of'from 270 C. .to 330 C.,' with a loss in weight 'bf not over 12%,neutralization being accomplished by means of an inorganic base. 5. Anew composition of matter, consisting of a neutralized'sulphate compoundof an unsaturated, saponifiable, fatty acid material, said unsaturated,saponiflable, fatty acid 'material having at least fi carbon atoms andless than 16 carf bon atomsin' the molecule, and derived by thermaldecomposition of a body obtained by: the oxidation of a relativelyhighly unsaturated, fatty body; said fatty body prior-to oxidation,being characterized byan iodine number of not less than-120 and not morethan 190, said oxidation being conducted at a; .temp erature range offrom rated, saponiflable, fatty acid material, said unsaturated,saponiiiable, fatty acid material having at least 6 carbon atoms andless than 16 carbon atoms in the molecule, and derivedby therspog msl arase in h tvl value d said thermal decomposition beingconducted at atemperaturerangefof from 270 C. to 330 C.', with a 7, A new compositionof matter, consisting of a sulphate compound of an unsaturated,saponiflable, fatty acid material having at least 6 carbon molecule,and'derived bythermal decomposition of 'a body obtained by the oxidationof sardine oil, said oxidation beingvconducted at. a temper- .aturerange of from 150 C. to 250 C. by means.

a value of not over two-thirds of the original iodine number andacorresponding increase in: A the acetyl value, and saidthermaldecomposition being conducted at a temperature range offff m.

40' over 12%, neutralization being accomplished by means of ammoniumhydroxide.

MELVIN GROOTE, BERNHABD xmsan.

neutralized sulphate compound of an unsatu- 10,;

mal decomposition of a body obtained by the is.

thirds oftlfe original iodine number and a corre- 20 loss-in weight-ofnot over 12%, neutralization oeing accomplished by means of .aninorganic atoms-andless than 16 carbon atoms in the 30.-

-of air untilthere is a drop in iodinefnumber to 270 Cato 330 0., with aloss in'weight of ot 40-

